Per unit
The system charges a single price for every unit of usage.
Volume
The system applies one rate to all units, based on which volume band the total usage falls into.
Tiered
The system splits usage across tiers and charges each tier at its own rate.
Comparing the three
Per unit is the simplest of the three and the baseline the other two are compared against. Tiered and volume both use brackets, but they resolve them differently: tiered splits usage across brackets so each portion is billed at its own rate, while volume finds a single bracket for the total quantity and bills every unit at that one rate. See tiered: what tiered pricing is and volume: what volume pricing is for that distinction worked through in detail.
Each pricing model page covers how it applies to point in time and period of time products, how to configure it, and its full field reference.